Anthraquinone derivatives



Patented Feb. 11, 1936 UNiT E'D STATES PATENT OFFICE ANTHRAQUINONEDERIVATIVES Hermann Hauser, Basel,

Riehen, near Basel,

and Max Bommer, Switzerland, assignors to firm Society of ChemicalIndustry in Basie,

Basel, Switzerland 2 Claims.

It has been found that compounds of the probable general formula inwhich R1 and R2 represent radicles capable of being vatted, at least oneof which is different from l-anthraquinonyl, are valuable anthraquinonederivatives.

These compounds may be made according to various processes. Thus forexample, 2 molecular proportions of similar or different compounds eachcontaining one amino-group and capable of being vatted, at least one. ofwhich is different from 1.-amino-anthraquinone, may be caused toreactwith 1 molecular proportion of 1,3-dihalogen-anthraquinone. Or 2molecular proportions of a 1,3-dihalogen-anthraquinone may be condensedwith 1 molecular proportion of a compound capable of being vatted andcontaining at least 2 amino-groups, and the product thus obtainedtransformed with 2 molecular proportions of any compound capable ofbeing vatted, but containing at least one amino group. Instead of the1,3-dihalogen-anthraquinones there may be used as initial products thecorresponding 1,3-diamino-anthraquinones, and on 1 molecular proportionof such a compound there may be caused to react 2 molecular proportionsof similar or different compounds, each containing one reactive halogenatom and capable of being vatted, at least one of which is differentfrom l-halogenanthraquinone. Or 2 molecular proportions of a1,3-diamino-anthraquinone may be condensed with 1 molecular proportionof a compound containing at least 2 reactive halogen atoms and capableof being vatted, and the product thus obtained transformed with 2molecular proportions of any compound capable of being vatted, butcontaining at least one reactive halogen atom.

The processes described above are preferably conducted in the presenceof a solvent of high boiling point, such as, for example, naphthalene,nitrobenzene, trichlorobe-nzene in the presence of acid binding agents,such as, for instance, anhydrous sodium acetate, potassium acetate,calcined alkali-carbonates, copper oxide, magnesium oxide, and in thepresence of catalysts, such as, for example, metallic copper and itscompounds. The compounds obtained in the above described manner arealready dyestufis themselves, but they may also serve as intermediateproducts for the manufacture of further dyestuffs.

Especially valuable dyestufis are obtained if the products obtainedaccording to the described processes with anthraquinone derivatives aretreated with condensing agents. There are thus formed-anthraquinonylamino-a a -anthrimidcarbazole vat dyestufis containing atthe most twice the carbazole grouping, and wherein at least one of theanthraquinonylamino radicles standing in uand 'y-position is difierentfrom the l-anthraquinonylamine As condensing agents there comeinto'consideration for example concentrated sulfuric acid,chlorosulfonic acid and fluor-sulfonic acid, aluminium chloride alone ormixed with alkali halides, or in the presence of organic bases, or asammonia double compound. In many cases it is advantageous to apply anafter-treatment of the dyestufis obtained with oxidizing agents, forexample hypochlorite.

As 1,3-dihalogen anthraquinones which may be used in the presentprocess, there come into consideration for example the1,3-dichloroanthraquinone, the 1,3-dibromo-anthraquinone, the1-chloro-3-bromo-anthraquinone, the 1- bromo-3-chloro-anthraquinone.Further also the 1,3-diamino-anthraquinone may be used in the presentprocess.

Compounds capable of being vatted containing one each or at least twoamino-groups and which may be caused to react with1,3-dihalogenanthraquinones are for example the following: 1- andZ-amino-anthraquinones, 1,4-, 1,5-, 1,8-diamino-anthraquinones,mono-benzoyl-diaminoanthraquinones, mono-acetyldiamino-anthraquinones,mono- (p-methoxy-) benzoyldiaminoanthraquinones,amino-nitro-anthraquinones, amino-dibenzanthrones, amino-pyranthrones,amino-anthanthrones, amino-anthrimides, amino-anthrimide-carbazoles,amino anthraquin- 50 mide-carbazoles, and the nitro derivatives of thesecompounds.

Compounds capable of being vatted containing one reactive halogen atomeach, or at least two reactive halogen atoms, and which may be caused toreact with the 1,3-diamino-anthraquinones, are for example thefollowing: 1- and 2-halogenanthraquinones, 1,4-, 1,5-, and1,8-dihalogenanthraquinones, halogen-benzoylamino-anthraquinones,halogen, acetylamino-anthraquinones, as well as halogen-pyranthrones,halogen-dibenzanthrones, halogen-dibenzpyrene-quinones,halogen-anthrimidecarbazoles, and the nitro derivatives of thesecompounds.

In dyeing, the new anthraquinone derivatives which may be producedaccording to the present process yield valuable shades of very goodfastness properties. They may also be used in dyeing in the form oftheir leuco compounds, such as for instance in the form of their leucoesters.

The following examples illustrate the invention:

Example 1 7.2 parts by weight of 1,3-dibromo-anthraquinone, 14 parts of1,5-monobenzoyl-diamino-anthraquinone, 8 parts of anhydrous sodiumacetate and parts of nitrobenzene are heated to boiling for 6 hours,during which the acetic acid which is formed distils. The whole isfiltered whilst still hot, the solid matter is Washed with nitrobenzeneand alcohol, and then extracted with boiling water, filtered and dried.There are obtained 17.7 parts of a red-brown crystalline powder of theprobable formula which, after precipitation from sulfuric acid of 96 percent strength at 0 0., yields on cotton powerful red-brown dyeings ofvery good fastness properties.

If in this example there is used instead of 1,5-mono-benzoyl-diamino-anthraquinone the iso-1,4monobenzoyl-diarnino-anthraquinone there is obtained a product whichdyes cotton powerful currant shades.

Example 2 18.3 parts of 1,3-dibromanthraquinone, 17.1 parts of1,5-monobenzoyl-diaminoanthraquinone, 10 parts of anhydrous sodiumacetate, 1 part of copper acetate and parts of nitro-benzene are heatedto boiling for 3 hours in a reflux apparatus. The new compound which hasseparated is isolated by filtering the mixture whilst still hot, washedwith nitrobenzene and alcohol, then boiled with water, filtered anddried. It is thus obtained in the form of small fine red needles whichdissolve in sulfuric acid of 97 per one-acridones, mono benzoyldiaminoanthricent strength to an olive brown solution. The new compound stillcontains a reactive halogen atom which can be replaced by anotherresidue in the following manner:

Parts Compounds 8 a-aminoanthraquinone 3 Anhydrous sodium acetate 3Copper acetate 1 Nitrobenzene 100 are heated to boiling for 18 hours ina reflux apparatus and the reaction product of the probable formula isisolated by filtering whilst still hot. It is a red crsytalline powderwhich dissolves in sulfuric acid of 97 per cent strength to a green toolive-green solution. After the new dyestuff has been reprecipitatedfrom its solution in concentrated sulfuric acid, it dyes cotton powerfulreddish-brown shades of very good fastness to washing and chlorine. Bystirring this compound for a short while with chlorosulfonic acid at50-55 C., diluting the chlorosulfuonic acid with sulfuric acid of 80 percent strength and pouring the whole onto ice there is obtained a newdyestuff of the probable formula which after treatment in known mannerwith a solution of sodium hypochlorite dyes cotton in a heated vatpowerful brown shades having a good resistance towards washing,kier-boiling and to chlorine.

Example 3 3.6 parts of 1,3-dibromanthraquinone, 9.4 parts ofamino-dibenzanthrone (obtainable by nitrating dibenzanthrone innitrobenzene, recrystallizing the product from concentrated sulfuricacid, vatting it with simultaneous reduction and recovering the productfrom the vat), 5 parts of anhydrous sodium acetate, 1 part of copperacetate.

and 170 parts of nitrobenzene are heated'to boiling for 22 hours in areflux apparatus; The sparingly soluble reaction product of the probableformula is isolated by filtering the reaction mixture at 70 C. and iswashed with nitrobenzene, then with alcohol and finally with boilingwater. The new dyestufi dissolves in sulfuric acid of. 9'7 per centstrength to a red-violet solution, from which bluegreen flakes areprecipitated by pouring into water. It dyes cotton dark green shadeswhich are distinguished above all by their good fastness to chlorine.

Example 4 18.3 parts of 1,3-dibromanthraquinone, 17.1 parts of1,4-monobenzoyl-diaminoanthraquinone,

' 10 parts of anhydrous sodium acetate, 1 part of copper acetate and 180parts of nitrobenzene are heated to boiling for 3 hours in a refluxapparatus; the nitrobenzene is then expelled by distillation with steamand the product is isolated by filtering the residue of thedistillation. After the new dyestuff has been reprecipitated from itssolution in concentrated sulfuric acid it dyes cotton weak currantshades. By further reaction with 1,5 monob-enzoyl diaminoanthraquinone ithe bromine atom in fl-position is also exchanged and there'is obtaineda dyestuff of the probable formula NHW I NH NH-C o-O which dyes cottonin a cold or heated vat violet brown shades of good fastness to Washingand to kier-boiling and of very food fastness to chlorine.

Example 5 4.8 parts of 1,3-diamino-anthraquinone, 17 parts ofl-benzoylamino-B-bromanthraquinone, 14 parts of anhydrous potassiumacetate, 1 part of copper acetate and 200 parts of nitrobenzene areheated to boiling for 36 hours in a reflux apparatus; the nitrobenzeneis then expelled by distillation with steam and the new product of theprobable formula C oo-rm o isolated by filtering the distillationresidue. It is purified by boiling with 5 times its weight ofnitrobenzene, stirring imtil cold and filtering cold. The new dyestufiis thus obtained in the form oi small needles. It dissolves at ordinarytemperature in sulfuric acid of 92 per cent. strength to a solutionwhich is at first dull violet but rapidly becomes blue. It dyes cottonin vat very fast reddish-brown shades.

Example 6 18.3 parts of 1,3-dibromanthraquinone, 17.1 parts of1,4-monobenzoyl-diaminoanthraquinone 10 parts of anhydrous sodiumacetate, 1 part of copper acetate and 180 parts of nitrobenzene areheated to boiling for 3 hours, whereupon the nitrobenzene is expelled bydistillation with steam and the reaction product, still containing onehalogen atom in the molecule, is isolated by filtration. It is solublein sulfuric acid of 97 per cent. strength to an olive-green solution.

7.7 parts of the product, 3 parts of l-aminoanthraquinone, 3 parts ofanhydrous sodium acetate, 0.5 part of copper acetate and 100 parts ofnitrobenzene are heated to boiling for 18 hours in a reflux apparatus.The reaction mixture is. allowed to cool to 50 C. whilst stirring andfiltered at this temperature; the solid matter con stituting the newproduct of the probable formula is washed with a small quantity ofnitrobenzene and boiled with Water. The product dissolves in sulfuricacid monohydrate to a grass-green solution. It dyes cotton in a vat fastwine-red shades.

Example 7 dissolves in sulfuric acid monohydrate to a green solution. Itdyes cotton in a vat fast red shades.

Example 8 '74 parts of 1,3-dibromanthraquinone, 23.8 parts of1,4-diaminoanthraquinone, 25 parts of anhydrous sodium acetate, 1 partof copper acetate, and 800 parts of nitrobenzene are heated to boilingfor 10 hours. The reaction product is separated by filtering thereaction mixture when cold, and washed with nitrobenzene and alcohol,and then extracted with boiling water and dried.

30 parts of the compound thus obtained, which still contains about 16per cent. of bromine, are

heated to boiling for 22 hours with 20 parts of l-aminoanthraquinone, 5parts of anhydrous sodium acetate, .10 parts of sodium carbonate, 1 partof copper chloride and 600 parts ofnitro-. benzene. The reaction productof the probable formula is filtered off at about 100 C. It is soluble insulfuric acid monohydrate to a pure green solution, from whichviolet-brown flakes are precipitated by pouring into water.

10 parts of this compound are then entered at about 100 0. into a fusionmass which is obtained by adding 20 parts of anhydrous aluminiumchloride to 40 parts of pyridine in such a way that the temperature doesnot essentially exceed 100 C. The temperature is then raised until thepyridine begins to boil slightly; .After 1 hour the fusion mass ispoured into an alkaline sodium hydrosulfite solution whereby the newdyestuff of the probable formula dissolves to. a .isolution. which isyellow-brown. The solution is then filtered so .as to. remove smallunvatted constituents and the dyestufi is separated from the filtrate byvigorous stirring in the air at ordinary temperature, and isolated byfiltration. It is obtained as a dark powder which dissolves inconcentrated sulfuric acid to a reddish brown-black solution. It dyescotton from the vat blackish-olive shades of very good fastnessproperties.

Example-9 74 parts of 1,3-dibromanthraquinone, 23.8 parts of1,5-diamino-anthr'aquinone, 25 parts of anhydrous sodium acetate, 1 partof copper acetate and 800 parts of nitrobenzene are heated to boilingfor 10 hours. The reaction product which separates in crystalline formis filtered when cold, washed with nitrobenz'ene and freed in usualmanner from inorganic constituents. It still contains about 17 per c entof bromine.

20 parts of the conversion product thus obtained are then heated toboiling for 24 hours with 20 parts of 1-amino-anthraquinone, parts ofsodium carbonate, 3 parts of sodium acetate, 1 part of copper chlorideand 200 parts of naphthalene. The whole is then allowed to coolslightly, and 200 parts of chlorobenzene are added. The reaction productis filtered at about 100, washed with chlorobenzene and worked up asusual. The compound thus obtained of the probable formula is thenfurther treated as follows:-

40 parts of aluminium chloride are added so slowly to 80 parts ofpyridine that no boiling of the pyridine occurs, parts of the above newcompound added, and the whole heated for about 1 hour in a refluxapparatus whilst stirring. The fusion mass is then poured into analkaline hydrosulfite solution whilst still hot, wherebythe new dyestufigoes into solution. The solution is then appropriately filtered toremove portions which have not been vatted, and the filtrate is treatedby vigorously stirring in the air. The dyestufi thus obtained oftheprobable formula dissolves in concentrated sulfuric acid to a bluesolution, from which brown flakes are precipitated by pouring intowater. It dyes cotton from a warm vat strong reddish-brown shades ofgood fastness properties.

Example 10 74 parts of 1,3-dibromanthraquinone, 23.3 parts of1,4-diaminoanthraquinone, 25 parts of anhydrous sodium acetate, 1 partof copper acetate, and 800 parts of nitrobenzene are heated to boilingfor 10 hours. When cold, the reaction product is filtered, the solidmatter is washed with nitro- 4 I @TZQJZ is filtered at about 80 C.,washed with nitrobenzene and afterwards with alcohol, and then extractedwith boiling water and a small quantity of dilute nitric acid, filteredand dried. By boiling up with nitrobenzene and hot filtration it isfreed from the 1:e-mono-benzoyldiaminoan thraquinone in excess. Theproduct dissolves in sulfuric acid monohydrate to a grass-greensolution.

10 parts of this compound are then entered at about 106 C. into a fusionmass which is obtained by adding parts of anhydrous aluminium chlorideto 40 parts of pyridine in such a way that the temperature does notessentially exceed 100 C. The temperature is then raised until thepyridine begins to boil slightly. After 1 hour the fusion mass is pouredinto an alkaline sodium hydrosulfite solution, whereby the new dyestuffdissolves to a yellow-brown solution. The dyestuff of the probableformula is precipitated by vigorously stirring in the air at ordinarytemperature, and filtered. It dissolves in concentrated sulfuric acid toan olivebrown solution. It dyes cotton from a vat powerful olive shadesof very good fastness properties.

Example 11 1 gram of the dyestuff made as described in the firstparagraph of Example 1 is well stirred with 5 cc. of caustic sodasolution of 36 B. and 100 cc. of water at a temperature of 30 C.; 2grams of hydrosulfite concentrated powder are added and vatting iscontinued for half-an-hour at the aforesaid temperature. The dye-bath isprepared with 3 cc. of caustic soda solution of 36 B., 1 gram ofhydrosulfite and sufficient water to make up the bath, including theparent vat to 2 liters; the parent vat is then added. The material isentered at 25-30 C., handled for a guarter-of-an-hour, 20 grams ofsodium chloride or calcined sodium sulfate are then added, and dyeing iscontinued for 1 hour at 25-30 C. The material is then wound off, allowedto oxidize in the air for half-an-hour, then rinsed, soured, againrinsed, and soaped at the boil. The material is thus dyed red-brown.

This application is a division of our U. S. application, Serial No.618,582, filed June 21, 1932 which has matured into U. S. Patent 'No.1,974,866, granted Sept. 25, 1934.

What we claim is:-

1. '-dianthraquinonyldiamino trianthrim'id dicarbazole vat-dyestufis ofthe general formula which product forms a dark powder dissolves inconcentrated sulfuric acid to a brownish solution and dyes cotton fromthe vat blackish-olive tints of very good fastness properties.

HERMANN HAUSER. MAX BOMMER.

